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CN100418419C - Novel use of herbicides - Google Patents

Novel use of herbicides Download PDF

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Publication number
CN100418419C
CN100418419C CNB018047475A CN01804747A CN100418419C CN 100418419 C CN100418419 C CN 100418419C CN B018047475 A CNB018047475 A CN B018047475A CN 01804747 A CN01804747 A CN 01804747A CN 100418419 C CN100418419 C CN 100418419C
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CN1404360A (en
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J·艾伦
W·T·鲁格
P·保特萨利斯
J-L·阿拉德
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Syngenta Participations AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Compounds of formula (I), wherein M is an alkali metal or alkaline earth metal; n is 1 or 2; r and s are each independently of the other 0, 1/2, 1, 1 1/2, 2, 2 1/2 or 3; and L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, tricholoromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, with the proviso that r is other than 1 1/2 when L is dioxane and s is 0, are suitable for use as herbicides in herbicide-tolerant crops of useful plants selected from maize, rice and soybeans.

Description

New use of herbicides
The present invention relates to N-[3-(2-three fluoro-ethyoxyls)-pyridine-2-base-sulfonyl]-N '-(4; 6-dimethoxy-pyrimidine-2-base)-the activity of weeding salt of urea is the useful crop of some herbicide-resistant; the corn of herbicide-resistant particularly, the purposes in soybean and the rice crop.
Use weed killer herbicide also can cause, for example depend on the concentration of weed killer herbicide and the mode of using the sizable poisoning of farming crop, the crop of cultivation, soil and weather conditions for example are exposed to time of illumination, the infringement that temperature and precipitation cause.Yet by using weed killer herbicide can realize optionally weeds control in crops, wherein by breeding method or genetic technique, useful crop more or less has been endowed the resistance to the phytotoxicity effect of weed killer herbicide.
The crop of the herbicide-resistant in the useful crop normally has resistance to the phytotoxicity effect of weed killer herbicide, and this acts on based on specific mechanism (for example acetolactate synthestase-inhibitor).Yet, show, although its effect to the farming crop of anti-certain weed killer herbicide has general pattern, this weed killer herbicide also is very variable using of they, in other words, according to the molecular structure and the amount of application of weed killer herbicide, on the resistance characteristics of raise crop, there is sizable difference.Correspondingly, certain weed killer herbicide often only is suitable for the certain species of a kind of raise crop.
For example described among the WO97/41218, to the weed killer herbicide Imazethapyr, the weed eradication quinoline, Fluoropyrimidinesulfuron, nicosulfuron, ethyl methyl, the weed eradication cigarette, the phytotoxicity effect of cigarette imidazoles grass and imazamox has the rice plants of tolerance.US4761373 discloses for example corn crop of the phytotoxicity effect of chlorsulfuron of anti-some sulphonyl ammonia.
Have now found that N-[3-(2-trifluoro ethoxy)-pyridine-2-base-sulfonyl]-some salt of N '-(4,6-dimethoxy-pyrimidine-2-base)-urea is to be particularly suitable for controlling weeds in being selected from the herbicide-resistant crop of corn, paddy rice and soybean.
Therefore, according to the method for control undesired plants growth in the herbicide-resistant crop in being selected from the useful crop of corn, rice and soybean that the invention provides a kind of recommendation, in this method with the compound of formula I:
Figure C0180474700111
Wherein
M is alkali metal or alkaline earth metal;
N is 1 or 2;
R and s independently are 0,1/2,1,11/2,2,21/2 or 3 separately; And
L is an ethyl acetate, acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, acetone, butanone, carrene, chloroform, trichloroethanes, oxolane, ether, 1, the 2-dimethoxy-ethane, dioxane, methyl tertiary butyl ether(MTBE), chlorobenzene, toluene or dimethylbenzene are administered to crop or are administered to its location with herbicidally effective amount.
M is as alkali metal or alkaline earth metal preferred sodium, potassium, magnesium or calcium in the context of the present invention.
The present invention includes the whole crystal modifications that form by formula I compound.
The compound of the preferred formula I of the method according to this invention is a dioxane for L wherein, the compound of oxolane or water.Also preferably wherein n be 1, M is in particular the compound of the formula I of sodium.
Also preferably wherein M be sodium, n is 1, r be 0 and s be 0 formula I compound.
Should mention especially also wherein for the method according to this invention that M is a sodium, n is 1, r be 0 and s be the amorphous solid of 0 formula I compound.For example, this amorphous solid can be used to prepare other crystal modification, for example C variant.
The utmost point is particularly preferred for the independent compound in the scope of formula I in the method according to this invention can mention compound below being selected from:
A) the B variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1, it is characterized in that X-ray powder pattern has d
Figure C0180474700112
/ intensity: in 10.0/; 9.2/ it is strong; 8.6/ very; 8.1/ a little less than; 7.2/ it is strong; 6.9/ it is strong; 6.4/ in; 5.82/ it is strong; 5.75/ it is strong; 5.64/ it is very strong; 5.53/ very; 5.13/ in; 4.97/ it is very strong; 4.65/ in; 4.30/ it is very strong; 4.22/ a little less than; 4.15/ very; 4.02/ a little less than; 3.94/ a little less than; 3.79/ in; 3.73/ a little less than; 3.68/ in; 3.61/ a little less than; 3.58/ a little less than; 3.52/ it is very strong; 3.42/ very; 3.37/ a little less than; 3.31/ very; 3.27/ very; 3.23/ a little less than; 3.18/ in; 3.08/ very; 3.03/ very; 2.95/ very; 2.87/ it is strong; 2.82/ very; 2.79/ very; 2.73/ very; 2.68/ very; 2.65/ very; 2.63/ very; 2.60/ a little less than; 2.57/ a little less than;
B) the J variant of formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1/2 and s be 0, it is characterized in that X-ray powder pattern has d
Figure C0180474700121
/ intensity: a little less than in the of 15.7/; 10.2/ it is very strong; 8.2/ a little less than; 7.8/ a little less than; 7.3/ a little less than; 6.7/ a little less than; 6.5/ very; 6.2/ in; 5.64/ very; 5.53/ a little less than; 5.42/ a little less than; 5.09/ a little less than; 4.96/ in; 4.86/ very; 4.60/ in; 4.37/ in; 4.24/ a little less than; 4.11/ it is very strong; 3.95/ very; 3.90/ a little less than; 3.81/ very; 3.71/ in; 3.62/ a little less than; 3.52/ very; 3.43/ it is strong; 3.37/ a little less than; 3.32/ very; 3.27/ a little less than; 2.94/ very; 2.82/ in;
C) the K variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 0, it is characterized in that X-ray powder pattern has d
Figure C0180474700122
/ intensity: a little less than in the of 13.4/; 10.1/ very; 9.3/ it is very strong; 7.8/ a little less than; 6.9/ very; 6.7/ very; 5.63/ very; 5.35/ in; 4.66/ a little less than; 4.44/ very; 4.35/ a little less than; 4.12/ it is strong; 3.94/ it is strong; 3.87/ very; 3.76/ a little less than; 3.61/ in; 3.49/ very; 3.40/ very;
D) the C variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1, it is characterized in that X-ray powder pattern has d
Figure C0180474700123
/ intensity: in 13.1/; 11.0/ it is very strong; 8.8/ a little less than; 7.7/ it is very strong; 7.2/ it is very strong; 7.0/ a little less than; 6.4/ a little less than; 6.2/ it is strong; 5.96/ a little less than; 5.90/ a little less than; 5.64/ it is strong; 5.47/ a little less than; 5.34/ in; 5.19/ a little less than; 4.79/ a little less than; 4.74/ in; 4.64/ very; 4.55/ it is strong; 4.47/ a little less than; 4.35/ it is strong; 4.26/ in; 4.13/ a little less than; 4.06/ very; 3.92/ it is very strong; 3.87/ a little less than; 3.79/ it is very strong; 3.67/ a little less than; 3.61/ in; 3.58/ it is strong; 3.47/ a little less than; 3.32/ very; 3.24/ in; 3.14/ a little less than; 3.12/ a little less than; 3.07/ a little less than; 3.04/ it is strong; 2.97/ very; 2.92/ very; 2.88/ a little less than; 2.82/ a little less than; 2.77/ very; 2.74/ very; 2.69/ a little less than; 2.66/ very; With
E) the I variant of formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1 and s be 1, it is characterized in that X-ray powder pattern has d
Figure C0180474700131
/ intensity: a little less than in the of 11.6/; 9.8/ very; 8.0/ it is very strong; 7.6/ in; 6.7/ it is strong; 6.4/ very; 6.3/ a little less than; 6.1/ very; 5.80/ in; 5.66/ very; 5.47/ it is strong; 5.12/ very; 5.08/ very; 4.84/ a little less than; 4.76/ a little less than; 4.47/ it is strong; 4.40/ a little less than; 4.21/ in; 4.19/ in; 4.15/ very; 4.00/ very; 3.93/ very; 3.84/ in; 3.72/ it is very strong; 3.58/ in; 3.52/ in; 3.32/ very; 3.28/ very; 3.25/ very; 3.11/ very; 3.07/ very; 2.95/ very; 2.86/ a little less than; 2.82/ very; 2.75/ very; 2.57/ a little less than; 2.49/ very.
Also preferred
A) the K variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 0, be sodium by M wherein, n is 1, L is an oxolane, r be 1/2 and s be formula I compound (J variant) dry in a vacuum preparation under 35 ℃ to 65 ℃ temperature of 0;
B) the C variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1, by the preparation of following method:
I) unbodied form (A variant) contacts with the air of 98% relative moisture basically, or
Be sodium to M wherein ii), n is 1, r be 0 and s be in the K variant of 0 formula I compound, be that 0.1: 1 to 0.4: 1 ratio adds entry with the ratio of water and K variant, separate then and under 30-90 ℃ the temperature under pressure 0.01 to 0.1 crust the dry product that obtains;
C) the B variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1, by being sodium to M wherein, n is 1, r and s are suc as formula in the defined formula I compound of I, with the ratio of water and this compound is that 0.5: 1 to 20: 1 ratio adds entry, filters, in dry filter residue preparation under pressure 0.01 to 0.5 crust under 30-90 ℃ the temperature, or preferably by being sodium to M wherein, n is 1, and L is an oxolane, r be 1/2 and s be in 0 the formula I compound (K variant), or be sodium to M wherein, n is 1, and L is an oxolane, r be 1/2 and s be in 0 the formula I compound (J variant), or be sodium to M wherein, n is 1, and L is an oxolane, r be 1 and s be in 1 the formula I compound (I variant), or be sodium to M wherein, n is 1, r be 0 and s be in 1 the formula I compound (C variant), with water and K, J, the ratio of I or C variant is that 0.5: 1 to 20: 1 ratio adds entry, filters, in dry filter residue preparation under pressure 0.01 to 0.5 crust under 30-90 ℃ the temperature.
Under the situation of K variant, should should be mentioned that especially that its astonishing high heating power is learned stability and nonhygroscopic character.The B variant also demonstrates the particularly high stability in the presence of water.This character is particularly conducive to the preparation of the preparation of active component.
The compound of formula I can be according to conventional method by with the compound of formula II:
Figure C0180474700141
At ethyl acetate, acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, acetone, butanone, carrene, chloroform, trichloroethanes, oxolane, ether, 1, the 2-dimethoxy-ethane, dioxane, methyl tertiary butyl ether(MTBE), chlorobenzene, in toluene or the dimethylbenzene, and the compound prepared in reaction of formula V:
Figure C0180474700142
Wherein M defines suc as formula I.
Being reflected at-20 ℃ and carrying out under 180 ℃ temperature of the compound of formula II and the compound of formula III preferably carried out 30-80 ℃ temperature range.
The compound of formula II and III can be by the stoichiometrical quantitative response that equates, but isocyanates slightly excessive may be favourable.
The preparation of starting compound formula II is described in the 232 067,29th page of EP-A-0 for example.The compound of formula III can according to, for example, with the compound of formula IV:
Figure C0180474700143
R wherein 1For-CH 2-phenyl or isopropyl, the compound that changes formula V by aqueous solution chlorination into prepares.
With this compound ammonia treatment, then sulfonamide and 30% sodium methoxide that obtains reacted.This reaction is known and is well known to those skilled in the art.
The preferred crystal modification of formula I compound is specifically developed method preparation according to the present invention.
For example, M is a sodium preparing wherein, n is 1, L is an oxolane, r be 1/2 and s be in the method for J variant of 0 formula I compound, to calculate by weight 4 of 5-25%, the anhydrous tetrahydrofuran solution of 6-dimethoxy-pyrimidine-2-isocyanates joins under 35-65 ℃ temperature in the suspension of anhydrous tetrahydro furan of 3-(2-three fluoro-ethyoxyls)-pyridine radicals-sulfonamide sodium salt of calculating by weight 15-35%.
Add 4, behind 6-dimethoxy-pyrimidine-2-isocyanates, stirred reaction mixture is finished up to conversion.The method is preferably carried out under 40-50 ℃ temperature.The J variant that so obtains can be separated from reactant mixture by filtering.
Being used to prepare wherein, M is a sodium, n is 1, r be 0 and s be following the carrying out of method of the K variant of 0 formula I compound: will calculate by weight 4 of 5-25%, the anhydrous tetrahydrofuran solution of 6-dimethoxy-pyrimidine-2-isocyanates joins under 35-65 ℃ temperature in the suspension of anhydrous tetrahydro furan of 3-(2-three fluoro-ethyoxyls)-pyridine radicals-sulfonamides sodium salt of calculating by weight 15-35%, filter, then the residue (J variant) of dry filter under the pressure of 30-90 ℃ temperature and 0.01 to 0.1 crust.
Add 4, behind 6-dimethoxy-pyrimidine-2-isocyanates, stirred reaction mixture is finished up to conversion.In the another kind of scheme of the method, preferably dry under the pressure of 40-60 ℃ temperature and 0.02 to 0.06 crust.
Being used to prepare wherein, M is a sodium, n is 1, r be 0 and s be following the carrying out of preparation method of the C variant of 1 formula I compound: perhaps unbodied form (A variant) is exposed in the air of relative moisture 98% basically, be that 0.1: 1 to 0.4: 1 ratio adds entry in the K variant perhaps with the ratio of water and K variant, filter, then that filter residue is dry under the pressure of 30-90 ℃ temperature and 0.01 to 0.1 crust.
For the preparation of C variant, the ratio of water and K variant can change in 0.1: 1 to 0.4: 1 scope; Preferred 0.1: 1 to 0.3: 1 especially ratio.The adding of water can be carried out under 5-40 ℃ temperature under 0-60 ℃ temperature especially.
The dry of C variant preferably carries out under the pressure of 40-60 ℃ temperature and 0.02 to 0.06 crust.
The C variant can also preferably prepare by the following method: with N-[(4; 6-dimethoxy-2-pyrimidine radicals) carbamoyl]-3-(2; 2; the 2-trifluoro ethoxy)-pyridine-2-sulfonamides joins in the sodium hydrate aqueous solution; by evaporating vacuum concentration down, the residue that so obtains is stirred with ether then, filter at 50 ℃; dry under 120 ℃ temperature, the unbodied basically salt (A variant) that then will obtain is exposed in the air of relative moisture 98%.
Being used to prepare wherein, M is a sodium, n is 1, L is an oxolane, r be 1 and s be following the carrying out of method of the I variant of 1 formula I compound: will calculate by weight 4 of 5-25%, the anhydrous tetrahydrofuran solution of 6-dimethoxy-pyrimidine-2-isocyanates joins under 0-30 ℃ temperature in the suspension of anhydrous tetrahydro furan of 3-(2-trifluoro ethoxy)-pyridyl sulfonamide sodium salt of calculating by weight 10-35%, then adds the water with respect to 3-(2-trifluoro ethoxy)-pyridyl sulfonamide sodium salt 1-20 molar equivalent.In this scheme, especially preferably add the water of 2-5 molar equivalent.
Being used to prepare wherein, M is a sodium, n is 1, r be 0 and s be following the carrying out of method of the B variant of 1 formula I compound: is that 0.5: 1 to 20: 1 ratio joins wherein that M is a sodium with water with water and described compound, n is 1, and L, r and s are suc as formula in the defined formula I compound of I, filter, then that filter residue is dry under the pressure of 30-90 ℃ temperature and 0.01 to 0.1 crust.
Following the carrying out of another kind of preparation method of preferred B variant: to M wherein is sodium, n is 1, r be 0 and s be in 0 the formula I compound (K variant), or be sodium to M wherein, n is 1, L is an oxolane, r be 1/2 and s be in 0 the formula I compound (J variant), or be sodium to M wherein, n is 1, L is an oxolane, r be 1 and s be in 1 the formula I compound (I variant), or be sodium to M wherein, n is 1, r be 0 and s be in 1 the formula I compound (C variant), with water and K, J, the ratio of I or C variant is that 0.5: 1 to 20: 1 ratio adds entry, filter, then dry filter residue under the pressure of 30-90 ℃ temperature and 0.01 to 0.1 crust.
Water can be under 0-80 ℃ temperature, particularly preferably in adding under 5-40 ℃ the temperature.The drying of filter residue can be carried out under the pressure of 30-90 ℃ temperature and 0.01 to 0.1 crust; Preferably under the pressure of 40-60 ℃ temperature and 0.02 to 0.06 crust, carry out.Particularly advantageous is that crystal seed with the B variant joins in the suspension so that quicken crystal growth.
Can be with the compound of formula I with unmodified form, promptly be used as weed killer herbicide with the form that obtains in synthetic, but preferably they for example are processed into usual way with the auxiliary agent that uses in preparation technique usually, direct sprayable or dilutable solution, wetting powder, soluble or dispersible powder, soluble or dispersible granula, pulvis and so-called " non-water flowable ".Particularly preferred composition is the form with soluble or dispersible granula according to the present invention, and composition comprises the crystal modification B of formula I compound.
The preparation that is suitable for formula I compound is for example, describes among the 9th to 13 page of the WO97/34485.As the character of composition, method of application, for example spraying, atomizing, dust, wetting, spread fertilizer over the fields or pour, be to select according to predetermined target and main environment.Formulation, it is the compound (active component) that composition, preparation or mixture comprise formula I, or the compound of at least a formula I and common one or more solid or liquor auxiliary agent, be to prepare with known method, for example, by with active component and formulation auxiliary agent, for example with the mixing and/or grind preparation of solvent or solid carrier homogenization.Can also in the preparation of formulation, use surface active cpd (surfactant).The example of solvent and solid carrier is for example, enumerates among the 6th page of the WO97/34485.
Depend on the character of the formula I compound of wanting processed preparation, suitable surface active cpd is to have the good dispersion and the nonionic of wettability, cation and/or anion surfactant and surfactant mixture.
The example of suitable anion, nonionic and cationic surfactant is for example, enumerates in WO97/34485 the 7th and 8 pages.
In addition, be generally used for the surfactant in the formulation technology, the special surfactant of in following document, describing: " McCutcheon washing agent and emulsifier yearbook " (" McCutcheon ' sDetergents and Emulsifiers Annual ") MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., " Tensid-Taschenbuch ", Carl Hanser Verlag, MunichNienna 1981, and M. and J.Ash, " surfactant complete works " (" Encyclopedia of Surfactants "), Vol.I-III, Chemical Publishing Co., New York, 1980-81 also is the preparation that is suitable for according to Herbicidal combinations of the present invention.
Herbicidal formulations contains usually calculates by weight 0.1 to 99%, particularly calculate by weight 0.1 to 95% weed killer herbicide, calculate by weight 0.1 to 99.9%, particularly calculate by weight 5 to 99.8% solid or liquid preparation auxiliary agent, and calculate by weight 0 to 25%, particularly calculate by weight 0.1 to 25% surfactant, although commercial product may preferably be formulated into concentrate, the end user uses the preparation of dilution usually.Composition can further comprise other composition, for example stabilizing agent, for example vegetable oil or epoxidized vegetable oil (epoxidation cocoa butter, rape oil or soya-bean oil), defoamer, silicone oil for example, preservative, viscosity modifier, adhesive, tackifier, and chemical fertilizer or other active component.
Usually with amount of application 0.001 to 0.5 kg/ha, particularly 0.005 to 0.25 kg/ha is used for crop or location to formula I compound.Can be determined by experiment the concentration that requires to realize Expected Results.It depends on the character of effect, the crop of cultivation and the stage of weed growth and use (position, time, method) and may change in wide scope as the function of those parameters.
The compound of formula I is the characteristic that demonstrates weeding and suppress the character of growth, and they can be used in the plantation of useful crop of herbicide-resistant, especially at corn, in the plantation of paddy rice and soybean.Term " crop " can be understood to include those results as the breeding method of routine or gene technology and be endowed chemical sproof those crops to weed killer herbicide or classes of herbicides.
The useful crop varieties that is particularly suitable for according to purposes of the present invention is the crop that those inhibition to acetolactate synthase (ALS) have resistance.Being used for producing the tissue culture technique of herbicide-resistant crop and the method for gene describes at for example EP-A-0 154 204.
People know already that in some enterobacteria and yeast the tolerance to sulfonylureas and imidazolinone herbicide is based on one or more sudden change in the gene, and this gene codified acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) also cause changing accordingly in the AHAS enzyme.For example, described the corn crop that the selection by plant cell cultures obtains among the United States Patent (USP) U.S.4 761 373, it has tolerance to the herbicidal concentrates that normally suppresses the corn crop growth.Tolerance is based on the modification in the AHAS zymoprotein.EP-A 257 993 described several A HAS-coding gene nucleotide sequence and altogether 7 derive from sequences, they have in nucleotide sequence and the correspondingly also improvement in corresponding amino acid sequence, have caused the tolerance to conventional sulfonylurea herbicide usage amount.This application also discloses the AHAS gene that makes those modifications can be embedded into method in the plant by means of engineered method.
People know that the AHAS enzyme is present in higher plant and the microorganism usually, for example saccharomyces cerevisiae or enterobacteria for example, in Escherichia coli and the salmonella typhimurium.In tobacco plant, the function of AHAS is that the gene by two not couplings is SuRA and SuRB coding.Those genes all are substantially the same (people such as Lee, EMBO J.7:1241-1248,1988) on nucleotide and amino acid levels.Yet Arabidopsis only has the single AHAS gene that has similarly been sorted fully.(people such as Mazur, " plant physiology " (Plant Physiol.) 85:1110-1117,1987).The comparison sheet of the nucleotide sequence of the AHAS gene in the higher plant understands that those zones demonstrate high reservation degree.Can determine the zone that at least 10 kinds of such height keep.
United States Patent (USP) U.S.5 013 659 has described the mutant strain that has the herbicide-resistant of variation at least one amino acid in one or more those reserve areas.Especially, extremely special amino acid is arranged in those zones, it is to have chemical sproofly by another amino acid whose substitutes, and finally causes crop to increase tolerance to weed killer herbicide under the situation of the catalytic activity that does not lose them simultaneously.The wherein sudden change of Miao Shuing or encoded to the cross-resistance of imidazolone and sulfonylureas perhaps has the special tolerance to sulfonylureas.
Can carry out mutagenesis in the cell/tissue step, or use sowing carry out mutagenesis (referring to, for example, EP-A 0 965 265).Preferably use conventional method about this point, as usually in the mutagenesis scope.
Such method as, for example Kueh and Bright described (Kueh, J.S.H. and Bright, S.W.J., Planta, 153, 166-171 (1981).Other mutagenesis method use N-methyl-N-nitrosourea and N-ethyl-N-nitrosourea (Fluhr, R. and Cseplo, A., Methods Enzymol.(Plant Mol.Biol.), 118,611-623 (1986)), ethyl methane sulfonate (Sebastian, S.A. wait the people, Crop Sci., 29, 1403-1408 (1989)) and azanol or hydrazine (Khamankar, Y.G., J. Maharashtra Agric.Univ., 14, 322-325 (1989)) and as mutagen.
In US-A-5 718 079, description is arranged based on the screening of the AHAS inhibitory action of using cell culture technology and the method for the mutant strain that selection has herbicide tolerant.Another method is the mutagenesis of seed, is promptly containing in the solution of AHAS inhibitor to cultivate in the first screen step.In second step, planting seed in soil, is sprayed with identical AHAS inhibitor then.Those normal developments and have normal phenotypic crop and be considered to being used for the kind that AHAS inhibitor under the various situations has resistance.
The controlled weeds of desire can be monocotyledonous and dicots weeds, Stellaria for example, garden nasturtium, bent grass, lady's-grass, Avena, setaria, mustard belongs to, Lolium, Solanum, barnyard grass, the Fischer grass, Monochoria vaginalis, arrowhead belongs to, and the wheat sparrow belongs to, amur foxtail belongs to, stone thatch Chinese sorghum, Rottboellia exaltata, Cyperus, abutilon, chrysanthemum harvest spp, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, clearvers, Viola and Veronica.
The compound of formula I preferably can mix with many other known weed killer herbicides, obtains thus, for example, the weeds of quite widening spectrum and under many circumstances with respect to the optionally increase of useful crop.
The invention still further relates to such mixture.The mixture of especially, following formula I compound is important:
Formula I compound+Acetochlor
Formula I compound+acifluorfen
Formula I compound+aclonifen
Formula I compound+alachlor
Formula I compound+amicarbazone
Formula I compound+atrazine
Formula I compound+azoles is decided humulone
Formula I compound+azimsulfuron
Formula I compound+flufenacet (BAY FOE 5043)
Formula I compound+benazolin
Formula I compound+benzyl ethyl methyl
Formula I compound+bentazone
Formula I compound+two careless ethers
Formula I compound+Brominal
Formula I compound+butachlor
Formula I compound+Ding Caote
The careless amine of formula I compound+block
Formula I compound+chlorimuron
Formula I compound+cinidon-ethyl (cinidon-ethyl)
Formula I compound+ether is yellow grand
Formula I compound+clethodim
Formula I compound+clefoxydim
Formula I compound+alkynes grass ester
Formula I compound+clomazones
Formula I compound+clopyralid
Formula I compound+cloransulammethyl
Formula I compound+cyhalofop-butyl
Formula I compound+cycloxydim
Formula I compound+2,4-drips
Formula I compound+2, the 4-Embutox
Formula I compound+dicamba
Formula I compound+diclofop
Formula I compound+diclosulam
The formula I compound+fast Methylsulfate of two benzene azoles
Formula I compound+dimethenamid
Formula I compound+S-dimethenamid
Formula I compound+amino second fluorine spirit
Formula I compound+diuron
Formula I compound+bactericide (EPTC)
Formula I compound+ethrel
Formula I compound+ethoxysulfuron
Formula I compound+fenclorim
Formula I compound+fentrazamide
Formula I compound+wheat straw volt
Formula I compound+fluzasulfuron
Formula I compound+fluazifop
Formula I compound+flufenazet
Formula I compound+flumetralim
Formula I compound+Flumetsulam
Formula I compound+fluoxaprop
Formula I compound+fluorine pyridine is yellow grand
Formula I compound+fluroxypyr
The careless fluorine of formula I compound+reach
Formula I compound+fluxofenim
Formula I compound+fomesafen
Formula I compound+formyl ammonia sulphur swells (foramsulfuron)
Formula I compound+careless ammonium phosphine
Formula I compound+glyphosate
Formula I compound+halosulfuronmethyl
Formula I compound+pyrrole fluorine chlorine standing grain spirit
Formula I compound+miaow grass ester
Formula I compound+weed eradication cigarette
Formula I compound+weed eradication quinoline
Formula I compound+Imazethapyr
Formula I compound+imazosulfuron
Formula I compound+imazamox
Formula I compound+iodine metsulfuron-methyl
Formula I compound+ioxynil
Formula I compound+isoxazole humulones
Formula I compound+Long Caote
Formula I compound+lactofen
Formula I compound+lenacil
Formula I compound+lorox
Formula I compound+Vi par
Formula I compound+methabenzthiazuron
Formula I compound+kill azoles
Formula I compound+metobromuron
Formula I compound+isopropyl methoxalamine
Formula I compound+S-isopropyl methoxalamine
Formula I compound+metosulam
Formula I compound+piperazine humulone
Formula I compound+metsulfuron-methyl
Formula I compound+ordram
Formula I compound+2 first, 4 chlorine
Formula I compound+NDA-402989
Formula I compound+nicosulfuron
Formula I compound+norflurazon
Formula I compound+oryzalin
Formula I compound+Evil humulones
Formula I compound+oxasulfuron
Formula I compound+oxacyclomefon
Formula I compound+Oxyfluorfen
Formula I compound+Pendimethalin
Formula I compound+phenmedipham
Formula I compound+Gao oxazole diclofop-methyls (R)
The careless amine of formula I compound+third
Formula I compound+Fluoropyrimidinesulfuron
Formula I compound+procarbazone sodium salt (procarbazone-sodium)
Formula I compound+prometryn
Formula I compound+Stam F-34
Formula I compound+propaquizafop
Formula I compound+prosulfuron
Formula I compound+pyraclonil (pyrazogyl)
Formula I compound+pyrazolate
Formula I compound+pyrazosulfuron
Formula I compound+pyridate
Formula I compound+KIH 6127
Formula I compound+pyrithiobac-sodium
Formula I compound+dichloro quinolinic acid
Formula I compound+quizalofop-ethyl
Formula I compound+rimsulfuron 25
Formula I compound+ethylenediamine tetra-acetic acid
Formula I compound+sethoxydim
Formula I compound+Simanex
Formula I compound+sulphur humulone
Formula I compound+sulphonyl azoles humulone
Formula I compound+glyphosate
Formula I compound+Sulfosulfuron
Formula I compound+tepraloxydim (tepraloxydim)
Formula I compound+Garagard
Formula I compound+terbutryn
Formula I compound+thiazfluron
Formula I compound+thiazopyr
Formula I compound+thiophene methyl
Formula I compound+benthiocarb
Formula I compound+tralkoxydim
Formula I compound+triallate
Formula I compound+triasulfuron
Formula I compound+trefanocide
Formula I compound+tritosulfuron (tritosulfuron)
Formula I compound+tribenuron-methyl
Formula I compound+Triclopyr
Formula I compound+fluorine amine is yellow grand
Formula I compound+anti-ester
With the material of formula I compound can also be form with ester or salt, for example at " agricultural chemicals handbook (The Pesticide Manual), the 11st edition, 1997, those materials of mentioning among the BCPC.
Now show the safener that some is known, for example safener of in following document, listing: US-A-5 041 157 surprisingly, US-A5 541 148, US-A-5 006 656, and EP-A-0094 349, and EP-A-0 551 650, EP-A-0 268 554, EP-A-0 375 061, and EP-A-0174 562, and EP-A-492 366, WO91/7874, WO94/987, DE-A-19612943, WO96/29870, WO98/13361, WO98/39297, WO98/27049, EP-A-0 716073, EP-A-0 613 618, and US-A-5 597 776 and EP-A-0 430 004 are suitable for the compound of formula I.Therefore the invention still further relates to a kind of be used to control dogstail and useful crop; corn particularly; the optionally Herbicidal combinations of weeds in the herbicide-resistant crop-planting of soybean and paddy rice; the weed killer herbicide and the safener (antagonist that comprise formula I; antipoison); said composition can be protected useful crop but not weeds, prevents the phytotoxicity effect of weed killer herbicide, and the purposes that relates to composition weeds in the herbicide-resistant crop of the useful crop of control.
Therefore recommended a kind of optionally Herbicidal combinations that is used for the herbicide-resistant crop of useful crop according to the present invention, wherein except common inert formulation auxiliary agent, carrier for example outside solvent and the wetting agent, comprises the mixture as the following substances of active component:
A) the formula I compound of herbicidally effective amount:
Figure C0180474700261
Wherein substituting group as defined above and
B) the formula S-I compound of weeding antagonism effective dose:
Figure C0180474700262
Wherein
Rs 1Be hydrogen or chlorine and
Rs 2Be hydrogen, C 1-C 8Alkyl, or by C 1-C 6Alkoxyl or C 3-C 6The C that alkenyloxy replaces 1-C 8Alkyl;
Or the compound of formula S-II:
Figure C0180474700263
Wherein
E 1Be nitrogen or methine;
Rs 3For-CCl 3, the phenyl that phenyl or halogen replace;
Rs 4And Rs 5Independently be hydrogen or halogen separately; With
Rs 6Be C 1-C 4Alkyl;
Or the compound of formula S-III:
Rs wherein 7And Rs 8Independently be separately hydrogen or halogen and
Rs 9, Rs 10And Rs 11Independently be C separately 1-C 4Alkyl;
Or the compound of formula S-IV:
Figure C0180474700272
Wherein
Rs 12It is group
Figure C0180474700273
Rs 13Be hydrogen, halogen, cyano group, trifluoromethyl, nitro, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl ,-COOH ,-COO-C 1-C 4Alkyl ,-CONRs 18Rs 19,-C (O)-C 1-C 4Alkyl, C (O)-phenyl, or by halogen, C 1-C 4Alkyl, methoxyl group, the phenyl that nitro or trifluoromethyl replace, or-SO 2NRs 20Rs 21Or-OSO 2-C 1-C 4Alkyl;
Rs 18, Rs 19, Rs 20And Rs 21Independently be hydrogen or C separately 1-C 4Alkyl, or
Rs 18And Rs 19Or Rs 20And Rs 21Form C together 4-C 6Alkylidene bridge, they can by oxygen, NH or-N (C 1-C 4Alkyl)-at interval;
Rs 14Be hydrogen, halogen, C 1-C 4Alkyl, trifluoromethyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group ,-COOH or-COO-C 1-C 4Alkyl;
Or Rs 13And Rs 14Form C together 3-C 4Alkylidene bridge, this bridge can be by halogen or C 1-C 4Alkyl replaces; Or Rs 13And Rs 14Form C together 3-C 4The alkenylene bridge, this bridge can be by halogen or C 1-C 4Alkyl replaces; Or Rs 13And Rs 14Form C together 4Alkylene dialkylene bridge, this bridge can be by halogen or C 1-C 4Alkyl replaces;
Rs 15And Rs 16Independently be hydrogen separately, C 1-C 8Alkyl, C 3-C 8Cycloalkyl, C 3-C 6Alkenyl, C 3-C 6Alkynyl, Or by C 1-C 4Alkoxyl or the C that is replaced by following formula 1-C 4Alkyl:
Figure C0180474700282
Or Rs 15And Rs 16Form C together 4-C 6Alkylidene bridge, this bridge can be by oxygen, sulphur, SO, SO 2, NH or-N (C 1-C 4Alkyl)-at interval;
Rs 22, Rs 23, Rs 24And Rs 25Independently be hydrogen separately, halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group ,-COORs 26, trifluoromethyl, nitro or cyano group, Rs 26Be hydrogen in each case, C 1-C 10Alkyl, C 1-C 4Alkoxy-C 1-C 4Alkyl, C 1-C 4Alkylthio group-C 1-C 4Alkyl, two-C 1-C 4Alkyl amino-C 1-C 4Alkyl, halogen C 1-C 8Alkyl, C 2-C 8Alkenyl, halogen C 2-C 8Alkenyl, C 3-C 8Alkynyl, C 3-C 7Cycloalkyl, halogen-C 3-C 7Cycloalkyl, C 1-C 8Alkyl-carbonyl, pi-allyl carbonyl, C 3- C7Naphthene base carbonyl, benzoyl, its be unsubstituted or on phenyl ring by three identical or different halogen, C of being selected from the most 1-C 4Alkyl, halogen-C 1-C 4Alkyl, halogen C 1-C 4Alkoxyl and C 1-C 4The substituting group of alkoxyl replaces; Or furyl or thienyl; Or by phenyl, halogenophenyl, C 1-C 4Alkyl phenyl, C 1-C 4Alkoxyl phenyl, halogen C 1-C 4Alkyl phenyl, halogen C 1-C 4Alkoxyl phenyl, C 1-C 6Alkoxy carbonyl group, C 1-C 4Alkoxy-C 1-C 8Alkoxy carbonyl group, C 3-C 8The alkenyl oxy carbonyl, C 3-C 8The alkynyloxy group carbonyl, C 1-C 8The alkylthio group carbonyl, C 3-C 8The alkenyl thio carbonyl, C 3-C 8Alkynyl group sulfenyl carbonyl, carbamoyl, list-C 1-C 4Alkylamino radical carbonyl or two-C 1-C 4The C of alkylamino radical carbonyl substituted 1-C 4Alkyl; Or the phenyl amino carbonyl, itself can be by three identical or different halogen, C of being selected from the most on phenyl ring 1-C 4Alkyl, halogen-C 1-C 4Alkyl, halogen C 1-C 4Alkoxyl and C 1-C 4The substituting group of alkoxyl replaces or is selected from following substituting group by one and replaces: cyano group and nitro, or itself can be by one or two C 1-C 4Dioxolanes-2-base that alkyl replaces, or itself can be by one or two C 1-C 4Diox-2-base that alkane-Ji replaces, or by cyano group, nitro, carboxyl or C 1-C 8Alkylthio group-C 1-C 8The C that alkoxy carbonyl group replaces 1-C 4Alkyl;
Rs 17Be hydrogen or C 1-C 4Alkyl;
Rs 27Be hydrogen, halogen, nitro, C 1-C 4Alkyl or methoxyl group;
Rs 28Be hydrogen, halogen, C 1-C 4Alkyl, trifluoromethyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group ,-COOH or-COO-C 1-C 4Alkyl;
Rs 29Be hydrogen, halogen, cyano group, nitro, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl ,-COOH ,-COO-C 1-C 4Alkyl ,-CONRs 30Rs 31, C (O)-phenyl, or by halogen, C 1-C 4The phenyl that alkyl, methoxyl group, nitro or trifluoromethyl replace, or-SO 2NRs 32Rs 33,-OSO 2-C 1-C 4Alkyl, C 1-C 6Alkoxyl, or by C 1-C 4The C that alkoxy or halogen replaces 1-C 6Alkoxyl, or C 3-C 6Alkenyloxy, or the C that is replaced by halogen 3-C 6Alkenyloxy, or C 3-C 6The alkynyloxy base; Rs wherein 30And Rs 31Independently be hydrogen or C separately 1-C 4Alkyl, or Rs 30And Rs 31Form C together 4-C 6Alkylidene bridge, this bridge can by oxygen, NH or-N (C 1-C 4Alkyl)-at interval; And Rs 32And Rs 33Independently be hydrogen or C separately 1-C 4Alkyl, or Rs 32And Rs 33Form C together 4-C 6Alkylidene bridge, this bridge can by oxygen, NH or-N (C 1-C 4Alkyl)-at interval;
Rs 34Be hydrogen, halogen, nitro, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl ,-COOH ,-COO-C 1-C 4Alkyl or CONRs 35Rs 36, Rs wherein 35And Rs 36Independently be hydrogen or C separately 1-C 4Alkyl, or Rs 35And Rs 36Form C together 4-C 6Alkylidene bridge, this bridge can by oxygen, NH or-N (C 1-C 4Alkyl)-at interval;
Rs 37Be hydrogen, halogen, C 1-C 4Alkyl ,-COOH ,-COO-C 1-C 4Alkyl, trifluoromethyl or methoxyl group, or Rs 34And Rs 37Form C together 3-C 4Alkylidene bridge;
Rs 38Be hydrogen, halogen or C 1-C 4Alkyl;
Rs 39Be hydrogen, halogen, C 1-C 4Alkyl ,-COOH ,-COO-C 1-C 4Alkyl, trifluoromethyl or methoxyl group;
Rs 40Be hydrogen, halogen, nitro, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl ,-COOH ,-COO-C 1-C 4Alkyl or CONRs 42Rs 43
Rs 41Be hydrogen, halogen or C 1-C 4Alkyl; Or Rs 40And Rs 41Form C together 3-C 4Alkylidene bridge;
Rs 42And Rs 43Independently be hydrogen or C separately 1-C 4Alkyl, or Rs 42And Rs 43Form C together 4-C 6Alkylidene bridge, this bridge can by oxygen, NH or-N (C 1-C 4Alkyl)-at interval;
Rs 44Be hydrogen, halogen, C 1-C 4Alkyl ,-COOH ,-COO-C 1-C 4Alkyl, trifluoromethyl or methoxyl group;
Rs 45Be hydrogen, halogen, nitro, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl ,-COOH ,-COO-C 1-C 4Alkyl or CONRs 46Rs 47Rs 46And Rs 47Independently be hydrogen or C separately 1-C 4Alkyl, or Rs 46And Rs 47Form C together 4-C 6Alkylidene bridge, this bridge can by oxygen, NH or-N (C 1-C 4Alkyl)-at interval;
Rs 48Be hydrogen, halogen, C 1-C 4Alkyl ,-COOH ,-COO-C 1-C 4Alkyl, trifluoromethyl or methoxyl group;
Rs 49Be hydrogen, halogen, nitro, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl ,-COOH ,-COO-C 1-C 4Alkyl or CONRs 50Rs 51
Rs 51And Rs 52Independently be hydrogen or C separately 1-C 4Alkyl, or Rs 51And Rs 52Form C together 4-C 6Alkylidene bridge, this bridge can be by oxygen, NH or quilt-N (C 1-C 4Alkyl)-at interval;
Or the compound of formula S-V:
Figure C0180474700311
Rs wherein 53And Rs 54Independently be C separately 1-C 6Alkyl or C 2-C 6Alkenyl; Or Rs 53And Rs 54Be together
Figure C0180474700312
Rs 55And Rs 56Independently be hydrogen or C separately 1-C 6Alkyl; Or Rs 53And Rs 54Be together
Figure C0180474700313
Rs wherein 55And Rs 56Independently be C separately 1-C 4Alkyl, or Rs 55And Rs 56Be together-(CH 2) 5-; Rs 57Be hydrogen, C 1-C 4Alkyl or
Figure C0180474700314
Or Rs 53And Rs 54Be together
Figure C0180474700315
Wherein
Rs 58, Rs 59, Rs 60, Rs 61, Rs 62, Rs 63, Rs 64, Rs 65, Rs 66, Rs 67, Rs 68, Rs 69, Rs 70, Rs 71, Rs 72And Rs 73Independently be hydrogen or C separately 1-C 4Alkyl;
Or the compound of formula S-VI:
Rs wherein 75Be hydrogen or chlorine and Rs 74Be cyano group or trifluoromethyl;
Or the compound of formula S-VII:
Figure C0180474700321
Rs wherein 76Be hydrogen or methyl;
Or the compound of formula S-VIII:
Figure C0180474700322
Wherein
R is 0 or 1;
Rs 77Be hydrogen or C 1-C 4Alkyl, it can be replaced by following groups: C 1-C 4Alkoxyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphinyl, C 1-C 4Alkyl sulphonyl, C 1-C 4Haloalkyl, C 1-C 4Halogenated alkoxy, C 1-C 4Halogenated alkylthio, C 1-C 4The haloalkyl sulfinyl, C 1-C 4Halogenated alkyl sulfonyl, nitro, cyano group ,-COOH, COO-C 1-C 4Alkyl ,-NRs 80Rs 81,-SO 2NRs 82Rs 83Or-CONRs 84Rs 85
Rs 78Be hydrogen, halogen, C 1-C 4Alkyl, trifluoromethyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy;
Rs 79Be hydrogen, halogen or C 1-C 4Alkyl;
Rs 80Be hydrogen, C 1-C 4Alkyl or C 1-C 4Alkyl-carbonyl;
Rs 81Be hydrogen or C 1-C 4Alkyl; Or
Rs 80And Rs 81Form C together 4-or the C5-alkylidene;
Rs 82, Rs 83, Rs 84And Rs 85 respectivelyFrom independently being hydrogen or C 1-C 4Alkyl; Or
Rs 82And Rs 83Together or Rs 84And Rs 85Independently be C together separately 4-or C5-alkylidene, one of them carbon atom can be substituted by oxygen or sulphur, or one or two carbon atom can by-NH-or-N (C 1-C 4Alkyl)-substitute;
E 2, E 3, E 4And E 5Independently be oxygen separately, sulphur, C (Rs 86) Rs 87, carbonyl ,-NH-,-N (C 1-C 8Alkyl)-, group
Figure C0180474700331
Rs 86And Rs 87Independently be hydrogen or C separately 1-C 8Alkyl; Or
Rs 86And Rs 87Be C together 2-C 6Alkylidene;
Rs 88And Rs 89Independently be hydrogen or C separately 1-C 8Alkyl;
Or Rs 88And Rs 89Be C together 2-C 6Alkylidene;
Rs 90Be Rs 91-O-, Rs 92-S-or-NRs 93Rs 94
Rs 91And Rs 92Independently be hydrogen separately, C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 1-C 4Alkoxy-C 1-C 8Alkyl, C 3-C 6Alkenyloxy-C 1-C 8Alkyl or phenyl-C 1-C 8Alkyl, wherein benzyl ring can be by halogen, C 1-C 4Alkyl, trifluoromethyl, methoxyl group, methyl mercapto, methylsulfinyl or methyl sulphonyl replace, or C 3-C 6Alkenyl, C 3-C 6Haloalkenyl group, phenyl-C 3-C 6Alkenyl, C 3-C 6Alkynyl, phenyl-C 3-C 6Alkynyl, oxetanyl, furyl or tetrahydrofuran base;
Rs 93Be hydrogen, C 1-C 8Alkyl, phenyl, phenyl-C 1-C 8Alkyl, wherein this benzyl ring can be by fluorine, chlorine, bromine, nitro, cyano group ,-OCH 3, C 1-C 4Alkyl or CH 3SO 2-replace C 1-C 4Alkoxy-C 1-C 8Alkyl, C 3-C 6Alkenyl or C 3-C 6Alkynyl;
Rs 94Be hydrogen, C 1-C 8Alkyl, C 3-C 6Alkenyl or C 3-C 6Alkynyl;
Or Rs 93And Rs 94Be C together 4-or C5-alkylidene, one of them carbon atom can be substituted by oxygen or sulphur, or one or two carbon atom can by-NH-or-N (C 1-C 4Alkyl)-substitute;
Rs 95And Rs 96Independently be hydrogen or C separately 1-C 8Alkyl; Or
Rs 95And Rs 96Form C together 2-C 6Alkylidene; And
Rs 97Be C 2-C 4Alkenyl or C 2-C 4Alkynyl; Precondition is:
A) at least one ring members E 2, E 3, E 4And E 5Be carbonyl, and the ring members adjacent with that or those group is group Wherein has only such group; And
B) two adjacent ring members E 2And E 3, E 3And E 4And E 4And E 5Can not be oxygen simultaneously;
Or the compound of formula S-IX:
Figure C0180474700341
Rs wherein 98Be hydrogen, C 1-C 6Alkyl, C 3-C 6Cycloalkyl, C 3-C 6Alkenyl or C 3-C 6Alkynyl; And
Rs 99, Rs 100And Rs 101Independently be hydrogen separately, C 1-C 6Alkyl, C 3-C 6Cycloalkyl or C 1-C 6Alkoxyl, condition are substituent R s 99, Rs 100And Rs 101One of be not hydrogen;
Or the compound of formula S-X:
Figure C0180474700342
E wherein 6Be nitrogen or methine, work as E 6N is 0,1 when being nitrogen, 2 or 3 and work as E 6N is 0,1 when being methine, 2,3 or 4, and Rs 102Be halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl, C 1-C 4Halogenated alkoxy, nitro, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphonyl, C 1-C 4Alkoxy carbonyl group, phenyl or phenoxy group, or separately by C 1-C 3Alkyl, C 1-C 3Haloalkyl, C 1-C 3Alkoxyl, C 1-C 3Halogenated alkoxy, halogen, phenyl or phenoxy group that cyano group or nitro replace;
Rs 103Be hydrogen or C 1-C 4Alkyl;
Rs 104Be hydrogen, C 1-C 4Alkyl, C 3-C 6Cycloalkyl, C 2-C 6Alkenyl, C 2-C 6Alkynyl, C 1-C 4Haloalkyl, C 2-C 6Haloalkenyl group, C 2-C 6The halo alkynyl, C 1-C 4Alkylthio group-C 1-C 4Alkyl, C 1-C 4Alkyl sulphonyl-C 1-C 4Alkyl, C 1-C 4Alkoxy-C 1-C 4Alkyl, C 1-C 4Alkenyloxy-C 1-C 4Alkyl or C 1-C 4Alkynyloxy base-C 1-C 4Alkyl;
Or the compound of formula S-XI:
Figure C0180474700351
E wherein 7Be oxygen or N-Rs 105And Rs 105It is the group of following formula
Figure C0180474700352
Rs wherein 106And Rs 107Independently be cyano group separately, hydrogen, C 1-C 4Alkyl, C 3-C 6Cycloalkyl, C 2-C 6Alkenyl, aryl, phenyl or heteroaryl, or separately by C 1-C 3Alkyl, C 1-C 3Haloalkyl, C 1-C 3Alkoxyl, C 1-C 3Halogenated alkoxy, halogen, phenyl, aryl or heteroaryl that cyano group or nitro replace;
Or the compound of formula S-XII:
Figure C0180474700353
E wherein 8Be oxygen, sulphur, sulfinyl, sulfonyl or methine,
Rs 108And Rs 109Independently be CH separately 2COOR S112Or COOR S113Or be the group of following formula together :-(CH 2) C (O)-O-C (O)-(CH 2)-, and Rs 112And Rs 113Independently be hydrogen separately, C 1-C 4Alkyl, C 2-C 4Alkenyl, C 2-C 6Alkynyl, C 3-C 6Cycloalkyl, C 1-C 4Haloalkyl, metal cation or ammonium cation; And
Rs 110And Rs 111Independently be hydrogen separately, halogen or C 1-C 4Alkyl;
Or the compound of formula S-XIII:
Figure C0180474700354
Rs wherein 114And Rs 115Independently be hydrogen separately, halogen or C 1-C 4-haloalkyl, Rs 116Be hydrogen, C 1-C 4Alkyl, C 3-C 4Alkenyl, C 3-C 4Alkynyl, C 1-C 4Haloalkyl, C 3-C 6Cycloalkyl, metal cation or ammonium cation;
E 9Be nitrogen, methine, C-F or C-Cl and
E 10Be the group of following formula:
Figure C0180474700361
Rs wherein 118, Rs 119, Rs 121And Rs 122Independently be hydrogen or C separately 1-C 4Alkyl;
Rs 117And Rs 120Independently be hydrogen separately, C 1-C 4Alkyl, C 3-C 4Alkenyl, C 3-C 4Alkynyl, C 1-C 4Haloalkyl, C 3-C 6Cycloalkyl, metal cation or ammonium cation;
Or the compound of formula S-XIV:
Rs wherein 123Be hydrogen, cyano group, halogen, C 1-C 4Alkyl, C 3-C 6Cycloalkyl, C 1-C 4Alkoxyl, C 1-C 4Alkoxy carbonyl group, C 1-C 4The alkylthio group carbonyl ,-NH-Rs 125-C (O) NH-Rs 126, aryl or heteroaryl, or separately by C 1-C 3Alkyl, C 1-C 3Haloalkyl, C 1-C 3Alkoxyl, C 1-C 3Halogenated alkoxy, halogen, aryl or heteroaryl that cyano group or nitro replace;
Rs 124Be hydrogen, cyano group, nitro, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl, C 1-C 4Alkylthio group; And
Rs 125And Rs 126Independently be C separately 1-C 4Alkyl, C 1-C 4Haloalkyl, C 3-C 4Alkenyl, C 3-C 4Alkynyl, C 3-C 4Cycloalkyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkyl sulphonyl, aryl or heteroaryl, or separately by C 1-C 3Alkyl, C 1-C 3Haloalkyl, C 1-C 3Alkoxyl, C 1-C 3Halogenated alkoxy, halogen, aryl or heteroaryl that cyano group or nitro replace;
Or the compound of formula S-XV:
Figure C0180474700371
Rs wherein 127And Rs 128Independently be hydrogen separately, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl, list-C 1-C 8-or two-C 1-C 8-alkyl amino, C 3-C 6Cycloalkyl, C 1-C 4Alkylthio group, phenyl or heteroaryl;
Rs 129Be hydrogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl, list-C 1-C 8-or two-C 1-C 8-alkyl amino, C 3-C 6Cycloalkyl, C 1-C 4Alkylthio group, phenyl, heteroaryl, OH, NH 2, halogen, two-C 1-C 4Amino-alkyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphonyl or C 1-C 4Alkoxy carbonyl group;
Rs 130Be hydrogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl, list-C 1-C 8-or two-C 1-C 8Alkyl amino, C 3-C 6Cycloalkyl, C 1-C 4Alkylthio group, phenyl, heteroaryl, cyano group, nitro, carboxyl, C 1-C 4-alkoxy carbonyl group, two-C 1-C 4Aminoalkyl, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphonyl, SO 2-OH, two-C 1-C 4Aminoalkyl sulfonyl or C 1-C 4The alkoxyl sulfonyl;
Rs 131Be hydrogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl, list-C 1-C 8-or two-C 1-C 8-alkyl amino, C 3-C 6Cycloalkyl, C 1-C 4Alkylthio group, phenyl, heteroaryl, OH, NH 2, halogen, two-C 1-C 4-aminoalkyl, pyrrolidines-1-base, piperidines-1-base, morpholine-1-base, C 1-C 4Alkylthio group, C 1-C 4Alkyl sulphonyl, C 1-C 4Alkoxy carbonyl group, phenoxy group, naphthoxy, phenyl amino, benzoyloxy or phenyl sulfonyloxy;
Or the compound of formula S-XVI:
Figure C0180474700372
Rs wherein 132Be hydrogen, C 4Alkyl, C 1-C 4Haloalkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl or C 1-C 4Alkoxy-C 1-C 4Alkyl;
Rs 133Be hydrogen, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl or C 1-C 4Alkoxyl and Rs 134Be hydrogen, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl or C 1-C 4Alkoxyl; Condition is Rs 133And Rs 134Can not be hydrogen simultaneously.
Be particularly preferred for being selected from following compound: formula S1.1 according to the safener of composition of the present invention
Figure C0180474700381
And the compound of formula S1.2
Figure C0180474700382
And the compound of formula S1.3
Figure C0180474700383
And the compound of formula S1.4
And the compound of formula S1.5
And the compound of formula S1.6
Figure C0180474700392
And the compound of formula S1.7
And the compound of formula S1.8
Figure C0180474700394
With formula S1.9
Cl 2CHCON(CH 2CH＝CH 2)(S1.9)，
With formula S1.10
Figure C0180474700395
With formula S1.11
Figure C0180474700401
With formula S1.12
Figure C0180474700402
With formula S1.13
Figure C0180474700403
Formula S1.1 is known to the compound of S1.13; and in " agricultural chemicals handbook (thePesticide Manual), the 11 edition, the Britain crop protection committee (British CropProtection Council); describe in 1997; entry number is respectively 61 (formula S1.1, benoxacors), 304 (formula S1.2; fenclorim); 154 (formula S1.3, cloquintocet), 462 (formula S1.4; mefenpyrdiethyl (mefenpyr-diethyl)); 377 formula S1.5, furilazole (furilazole)), 363 (formula S1.8; fluxofenim); 213 (formula S1.9, allyl dichloride amine) and 350 (formula S1.10, flurazoles).The compound of formula S1.11 is called as MON4660 (Monsanto), and is for example describing among the EP-A-0 436 483.
The compound of formula S1.6 (AC304415) is for example being described among the EP-A-0 613 618, and the compound of formula S1.7 is described in DE-A-2948535.The compound of formula S1.12 is described in DE-A-4331448, and the compound of formula S1.13 is described in DE-A-3525205.
The following examples further illustrate the present invention, but do not limit the present invention.Example of formulations:
F1. dressing granula
a) b) c)
Formula I compound 0.1% 5% 15%
Polyethylene glycol MW 200 1.0% 2% 3%
The silicic acid of high degree of dispersion 0.9% 1% 2%
Inorganic carrier 98.0% 92% 80%
(diameter 0.1-1mm)
CaCO for example 3Or SiO 2
The active component of fine gtinding is applied in blender equably with on the moistening carrier of polyethylene glycol.Obtain non-dusting dressing granula by this way.
F2. Ji Ya granulaA) d c b)))
Formula I compound 0.1% 3% 5% 15%
Sodium lignin sulfonate 1.5% 2% 3% 4%
Carboxymethyl cellulose 1.4% 2% 2% 2%
Kaolin 97.0% 93% 90% 79%
Active component is mixed with auxiliary agent and grind, then that the mixture water is moistening.With the mixture extrusion molding, and dry in air flow.
F3. pulvisA) c b))
The compound of formula I 0.1% 1% 5%
Talcum powder 39.9% 49% 35%
Kaolin 60.0% 50% 60%
Obtain the dust agent that can use by active component and carrier being mixed be incorporated in to grind in the suitable grinding machine.
Embodiment F 4: the preparation of the wettable granula of formula I compound:
Following material is mixed, uses commercially available grinding machine to grind then:
The crystal modification A of the compound of 75% formula I:
4% nekal salt
8% sodium lignin sulfonate
0.5% silicone antifoam agent
Add to 100% silica
Then, the water of calculating by weight 22-26% is added in the mixture, carries out granulation.After being dried to residual moisture content＜4.5% on the commercially available continuous dryer,, obtain comprising the granula of the crystal modification C form of formula I compound with the particle diameter of to 0.4 to 1.6 millimeter of the granula that obtains screening (vibration/drum screen).
Embodiment F 5: the preparation of the wettable granula of formula I compound:
Following material is mixed, uses commercially available grinding machine to grind then:
The crystal modification B of 75% formula I compound
4% nekal salt
8% sodium lignin sulfonate
0.5% silicone antifoam agent
Add to 100% silica
Then, the water of calculating by weight 18-20% is added in the mixture, carries out granulation.After being dried to residual moisture content＜4.5% on the commercially available continuous dryer,, obtain comprising the granula of the crystal modification B form of formula I compound with the particle diameter of to 0.4 to 1.6 millimeter of the granula that obtains screening (vibration/drum screen).
Embodiment F 6: the preparation of the wettable granula of formula I compound:
Following material is mixed, uses commercially available grinding machine to grind then:
The crystal modification K of 75% formula I compound
4% nekal salt
8% sodium lignin sulfonate
0.5% silicone antifoam agent
Add to 100% silica
Then, the water of calculating by weight 43-48% is added in the mixture, carries out granulation.After being dried to residual moisture content＜4.5% on the commercially available continuous dryer, the particle diameter with to 0.4 to 1.6 millimeter of the granula that obtains screening (vibration/drum screen) obtains comprising the crystal modification B of formula I compound and the granula of crystal modification C form.
X-ray powder photograph collection of illustrative plates provides the d value (interplanar distance) of described crystal modification, X ray reflection bond strength and the angle of diffraction 2 θ (instrument-special).
The mensuration of X-ray powder pattern is that the Guiniercamera FR 552 usefulness CuKalphal rays with Enraf-Nonius company carry out.The pattern that uses the Scanpi-program appraisal on X line film, to write down with the Line-Scanner LS-18 of Johansson company.
Preparation embodiment:
Embodiment P1: formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1/2 and s be the preparation of 0 (J variant):
With 40 grams 4,300 gram oxolane (anhydrous) solution of 6-dimethoxy-pyrimidine-2-isocyanates join 210 of 59 gram 3-(2-trifluoro ethoxy)-pyridyl sulfonamide sodium salts and restrain in the suspension of anhydrous tetrahydro furans under 40-45 ℃ temperature.Finish up to conversion at 40 ℃ of following stirred reaction mixtures then.
At last by filtering and obtaining the J variant with the anhydrous tetrahydro furan washing.
Table R1: the X-ray powder collection of illustrative plates of variant J:
2 θ [°] d
Figure C0180474700431
Intensity
5.6 a little less than in the of 15.7
8.6 10.2 is very strong
10.7 a little less than in the of 8.2
11.3 a little less than in the of 7.8
12.1 a little less than in the of 7.3
13.1 a little less than in the of 6.7
13.6 6.5 very a little less than
14.4 in 6.2
15.7 5.64 very a little less than
16.0 a little less than in the of 5.53
16.3 a little less than in the of 5.42
17.4 a little less than in the of 5.09
17.9 in 4.96
18.2 4.86 very a little less than
19.3 in 4.60
20.3 in 4.37
21.0 a little less than in the of 4.24
21.6 4.11 is very strong
22.5 3.95 very a little less than
22.8 a little less than in the of 3.90
23.3 3.81 very a little less than
24.0 in 3.71
24.5 a little less than in the of 3.62
25.3 3.52 very a little less than
26.0 the last 3.43
26.4 a little less than in the of 3.37
26.8 3.32 very a little less than
27.3 a little less than in the of 3.27
30.4 2.94 very a little less than
31.7 in 2.82
Embodiment P2: formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 0 (K Variant) preparation:
Under the pressure of 60 ℃ temperature and 0.04 crust,, obtain the K variant with the J variant drying of embodiment P1.This crystal habit is anhydrous and solvent-free: thermogravimetry shows that weightlessness is still less than 0.1 weight % under up to 175 ℃ temperature.
Table R2: the X-ray powder pattern of variant K:
2 θ [°] d
Figure C0180474700441
Intensity
6.6 a little less than in the of 13.4
8.8 10.1 very a little less than
9.5 9.3 is very strong
11.4 a little less than in the of 7.8
12.9 6.9 very a little less than
13.3 6.7 very a little less than
15.7 5.63 very a little less than
16.6 in 5.35
19.0 a little less than in the of 4.66
20.0 4.44 very a little less than
20.4 a little less than in the of 4.35
21.5 the last 4.12
22.6 the last 3.94
22.9 3.87 very a little less than
23.7 a little less than in the of 3.76
24.6 in 3.61
25.5 3.49 very a little less than
26.2 3.40 very a little less than
Embodiment P3: formula I compound, wherein M is a sodium, and n is 1, and L is an oxolane, r Be 1 and s be the preparation of 1 (I variant):
With 19.9 grams 4,350 gram oxolane (anhydrous) solution of 6-dimethoxy-pyrimidine-2-isocyanates join under 25 ℃ temperature in the suspension of 200 milliliters of anhydrous tetrahydro furans of 34.2 gram 3-(2-trifluoro ethoxy)-pyridyl sulfonamide sodium salts.Finish up to conversion at 25 ℃ of following stirred reaction mixtures then.Add 10 gram water then, and mixture was stirred 18 hours.At last by filtering and obtaining the I variant with the anhydrous tetrahydro furan washing.
Table R3: the X-ray powder pattern of variant I:
2 θ [°] d
Figure C0180474700451
Intensity
7.6 a little less than in the of 11.6
9.0 9.8 very a little less than
11.0 8.0 is very strong
11.6 in 7.6
13.3 the last 6.7
13.7 6.4 very a little less than
14.0 a little less than in the of 6.3
14.4 6.1 very a little less than
15.3 in 5.80
15.6 5.66 very a little less than
16.2 the last 5.47
17.3 5.12 very a little less than
17.4 5.08 very a little less than
18.3 a little less than in the of 4.84
18.6 a little less than in the of 4.76
19.8 the last 4.47
20.1 a little less than in the of 4.40
21.1 in 4.21
21.2 in 4.19
21.4 4.15 very a little less than
22.2 4.00 very a little less than
22.6 3.93 very a little less than
23.2 in 3.84
23.9 3.72 is very strong
24.8 in 3.58
25.3 in 3.52
26.9 3.32 very a little less than
27.2 3.28 very a little less than
27.5 3.25 very a little less than
28.7 3.11 very a little less than
29.0 3.07 very a little less than
30.2 2.95 very a little less than
31.2 a little less than in the of 2.86
31.7 2.82 very a little less than
32.6 2.75 very a little less than
34.9 a little less than in the of 2.57
36.0 2.49 very a little less than
Embodiment P4: formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1 (B Variant) preparation:
The K variant of 100 grams according to embodiment P2 preparation suspended 15 minutes in 230 gram water, preferably 1-3 is restrained B variant crystal seed then and dope, then suspension is stirred under 20-25 ℃ temperature,, at this moment optionally obtain the B variant up to converting.Then filtering suspension liquid and under the pressure of 60 ℃ temperature and 0.04 crust with filter residue and drying to constant weight.
Table R4: the X-ray powder pattern of variant B:
2 θ [°] d
Figure C0180474700471
Intensity
8.9 in 10.0
9.6 the last 9.2
10.3 8.6 very a little less than
11.0 a little less than in the of 8.1
12.2 the last 7.2
12.9 the last 6.9
13.8 in 6.4
15.2 the last 5.82
15.4 the last 5.75
15.7 5.64 is very strong
16.0 5.53 very a little less than
17.3 in 5.13
17.8 4.97 is very strong
19.1 in 4.65
20.6 4.30 is very strong
21.0 a little less than in the of 4.22
21.4 4.15 very a little less than
22.1 a little less than in the of 4.02
22.5 a little less than in the of 3.94
23.4 in 3.79
23.8 a little less than in the of 3.73
24.2 in 3.68
24.6 a little less than in the of 3.61
24.8 a little less than in the of 3.58
25.3 3.52 is very strong
26.0 3.42 very a little less than
26.4 a little less than in the of 3.37
26.9 3.31 very a little less than
27.3 3.27 very a little less than
27.6 a little less than in the of 3.23
28.0 in 3.18
28.9 3.08 very a little less than
29.4 3.03 very a little less than
30.3 2.95 very a little less than
31.2 the last 2.87
31.7 2.82 very a little less than
32.1 2.79 very a little less than
32.7 2.73 very a little less than
33.4 2.68 very a little less than
33.8 2.65 very a little less than
34.0 2.63 very a little less than
34.5 a little less than in the of 2.60
34.9 a little less than in the of 2.57
In a similar fashion also can be with crystal form A, C, F, I and J are converted into the B form, also by realizing with these crystalline forms of wet with solvent.The amount of water can be improved a little in the case.
Embodiment P5: formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 0 (C Variant) preparation:
The K variant of 100 grams according to embodiment P2 preparation mixed 3 hours with 20 gram water, dry under the pressure of 60 ℃ of temperature and 0.04 crust then.
Table R5: the X-ray powder pattern of variant C:
2 θ [°] d
Figure C0180474700491
Intensity
6.7 in 13.1
8.1 11.0 is very strong
10.1 a little less than in the of 8.8
11.4 7.7 is very strong
12.2 7.2 is very strong
12.7 a little less than in the of 7.0
13.9 a little less than in the of 6.4
14.3 the last 6.2
14.9 a little less than in the of 5.96
15.0 a little less than in the of 5.90
15.7 the last 5.64
16.2 a little less than in the of 5.47
16.6 in 5.34
17.1 a little less than in the of 5.19
18.5 a little less than in the of 4.79
18.7 in 4.74
19.1 4.64 very a little less than
19.5 the last 4.55
19.9 a little less than in the of 4.47
20.4 the last 4.35
20.8 in 4.26
21.5 a little less than in the of 4.13
21.9 4.06 very a little less than
22.7 3.92 is very strong
23.0 a little less than in the of 3.87
23.5 3.79 is very strong
24.2 a little less than in the of 3.67
24.6 in 3.61
24.9 the last 3.58
25.7 a little less than in the of 3.47
26.9 3.32 very a little less than
27.5 in 3.24
28.4 a little less than in the of 3.14
28.6 a little less than in the of 3.12
29.1 a little less than in the of 3.07
29.3 the last 3.04
30.1 2.97 very a little less than
30.6 2.92 very a little less than
31.0 a little less than in the of 2.88
31.7 a little less than in the of 2.82
32.3 2.77 very a little less than
32.7 2.74 very a little less than
33.3 a little less than in the of 2.69
33.7 2.66 very a little less than
Embodiment P6: amorphous basically formula I compound, wherein M is a sodium, n is 1, r Be 0 and s be the preparation of 0 (A variant):
Under 20 ℃ temperature, with 1.56 gram N-[(4,6-dimethoxy-2-pyrimidine radicals) carbamoyl]-3-(2,2, the 2-trifluoro ethoxy)-pyridine-2-sulfuryl amine joins in 40 milliliter of 0.1 N sodium hydrate aqueous solution.Reactant mixture was stirred 18 hours down at 20 ℃.The residue that will obtain after vacuum evaporation concentrates stirs with ether under 50 ℃, and filters.The material that goes out by dry filter under rising temperature (＞120 ℃) obtains the A variant.
Embodiment P7: from A variant preparation I compound, wherein M is a sodium, and n is 1, and r is 0 and s be 0 (C variant):
Under 20 ℃ temperature, the crystallization of A variant is exposed to 98% relative air humidity 4 hours.Obtain having the C variant of the crystallographic data that provides among the embodiment P5.
Embodiment P8: formula I compound, wherein M is a sodium, and n is 1, and r is 2, and L is a dioxy Six rings and s are the preparation of 0 (G variant):
Under 20 ℃, with 15 grams, for example, the A variant for preparing according to embodiment P6 stirred 21/2 day in 85 gram dioxane, then mixture was filtered.Obtain G variant after the filtration, have the X-ray crystallography data that provide among the table R8 as filter residue.
Table R8: the X-ray powder pattern of variant G:
2 θ [°] d
Figure C0180474700511
Intensity
5.8 the last 15.3
7.0 12.7 very a little less than
8.4 a little less than in the of 10.5
11.1 in 7.9
12.8 in 6.9
13.4 6.6 very a little less than
14.3 6.2 is very strong
14.9 in 5.96
17.4 in 5.08
17.8 a little less than in the of 4.98
18.3 in 4.84
19.3 in 4.60
19.7 in 4.51
19.8 4.47 very a little less than
20.8 a little less than in the of 4.27
21.0 in 4.23
22.3 in 3.98
22.7 in 3.91
23.3 a little less than in the of 3.81
23.9 the last 3.71
24.4 in 3.65
24.9 a little less than in the of 3.57
25.4 in 3.50
26.2 3.39 very a little less than
26.7 a little less than in the of 3.33
28.9 3.08 very a little less than
29.5 3.02 very a little less than
30.5 a little less than in the of 2.93
Embodiment P9: formula I compound, wherein M is a sodium, and n is 1, and r is 1, and L is a dioxy six Ring and s are the preparation of 0 (F variant):
By will be exposed to according to the G variant of embodiment P8 preparation 20-25 ℃ and 50% relative air humidity following 8 days of condition, obtain the F variant.
Table 9: the X-ray powder collection of illustrative plates of variant G:
2 θ [°] d
Figure C0180474700521
Intensity
6.0 14.7 very a little less than
7.0 12.6 very a little less than
8.1 in 10.9
11.4 in 7.8
12.0 7.4 very a little less than
12.7 a little less than in the of 7.0
13.4 a little less than in the of 6.6
14.3 a little less than in the of 6.2
16.2 the last 5.45
18.0 in 4.91
18.4 a little less than in the of 4.83
18.6 4.76 very a little less than
20.8 4.28 very a little less than
21.7 a little less than in the of 4.10
22.2 4.00 very a little less than
23.7 3.75 is very strong
24.7 3.60 very a little less than
Biology embodiment
Embodiment B 1: to the postemergence weed control effect of corn and soybean
In the greenhouse, to test crop cultivates in standard soil in plastic basin, spray to the aqueous suspension of 3-leaf phase at 2-with the test compound of formula I, this aqueous suspension is by according to embodiment F 4,75% the wettable granula preparation of F5 or F6, corresponding to concentration is 30,15 and 7.5 gram active component/hectares (500 premium on currency/hectare).Under optimum condition, in the greenhouse, allow trial crops grow then.
After about 3 weeks, test is estimated.In these trials, the trial crops that can tolerate the weed killer herbicide (ALS-inhibitor) of inhibition acetolactic acid-synzyme demonstrates the good tolerance to the phytotoxicity effect of formula I compound, particularly for formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1/2 and s be the good tolerance of the phytotoxicity effect of 0 (J variant).
Embodiment B 2: to the postemergence weed control effect of rice
With the weeds sowing, and in plastic channel, in water saturated soil, cultivate.Sowing rice plant, and separate growth with weeds, after 10 days with its transfer in the plastic channel that contains weeds.Then the form of test compound with aqueous suspension is administered on the plant.Use one day after, with 3 centimetres (Rice System) of water level rising.
In the greenhouse, allow trial crops grow then under optimum conditions.After about 21 days (not effect of 0% expression, 100% expression plant is dead fully) estimated in test.In these trials, the trial crops that can tolerate inhibition acetolactic acid-synzyme weed killer herbicide (ALS-inhibitor) also demonstrates the good tolerance to the phytotoxicity effect of formula I compound, particularly for formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1/2 and s be the good tolerance of the phytotoxicity effect of 0 (J variant).
The embodiment of the good selectively acting of formula I compound provides in table B1.
For with prior art relatively, carried out the test of compound Sulfometuron Methyl (be known in " agricultural chemicals handbook (ThePesticide Manual), the 10th edition, the Britain crop protection committee (the BritishCrop Protection Council), the 931st page).Sulfometuron Methyl belongs to the ALS-inhibitor with formula I compound identical type.Formula I compound and Sulfometuron Methyl are tested with the amount of application of 8 gram/hectares.
The rice varieties of employed tolerance ALS-inhibitor is Oryza sativa, Lin Nai (Linnaeus) title: SPCW-1, deposit number ATCC 97523, preservation person: Louisiana State Univ.Agricultural and Mechanical CollegeIsolation:
Kind Lemont " what use is conventional rice varieties.
Table B1: act on behind formula I compound (J variant) and the seedling of Sulfometuron Methyl to paddy rice:
Figure C0180474700541
The weeds title The leaf phase when using Height when using (cm)
Behind barnyard grass 1.0 leaves (ECHCG 1) 1.5 6
Behind barnyard grass 3.0 leaves (ECHCG 3) 3 25
Monochoria vaginalis (MOOVA) 2 1
Herba Cyperi Glomerati (CYPSE) 3 11
The result of table B1 shows that under the amount of application of being tested, two kinds of sulfonylureas all destroy " Lemont " rice varieties and the weeds of routine.Therefore with such amount of application, these two kinds of compounds are not to be suitable in the rice varieties of routine is cultivated Selective Control weeds.Similarly, the paddy rice ATCC 97523 of tolerance ALS-inhibitor is almost ruined (95% phytotoxicity) entirely by Sulfometuron Methyl, and with the formula I compound that 8 gram/hectares are used, only causes the phytotoxicity of this rice varieties 40% surprisingly.Therefore formula I compound is particularly suitable for tolerating the rice crop of ALS, and structurally with the closely-related sulfonylureas Sulfometuron Methyl of formula I compound, then be not suitable for this crop fully.

Claims (6)

1. the method for a control undesired plants growth in the crop of the tolerance inhibitor of acetolactate synthetase weed killer herbicide of the useful crop that is selected from corn, paddy rice and soybean, in the method with the formula I compound of crystal form:
Figure C018047470002C1
Wherein
M is alkali metal or alkaline earth metal;
N is 1 or 2;
R and s independently are 0,0.5,1,1.5,2,2.5 or 3 separately; And
L is ethyl acetate, acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, acetone, butanone, carrene, chloroform, trichloroethanes, oxolane, ether, 1,2-dimethoxy-ethane, dioxane, methyl tertiary butyl ether(MTBE), chlorobenzene, toluene or dimethylbenzene
Amount of application with 0.001-0.5kg/ha is administered to crop or its location.
2. according to the process of claim 1 wherein, in formula I, M is a sodium, potassium, magnesium or calcium.
3. according to the process of claim 1 wherein, in formula I, L is dioxane or oxolane.
4. according to the process of claim 1 wherein, in formula I, n is 1, and M is a sodium.
5. according to the process of claim 1 wherein, in formula I, M is a sodium, and n is 1, r be 0 and s be 0.
6. according to the process of claim 1 wherein that the compound of general formula I is selected from:
A) the B variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1,
It is characterized in that having following X-ray powder pattern:
2 θ [°] d
Figure C018047470003C1
Intensity
8.9 in 10.0
9.6 the last 9.2
10.3 8.6 very a little less than
11.0 a little less than in the of 8.1
12.2 the last 7.2
12.9 the last 6.9
13.8 in 6.4
15.2 the last 5.82
15.4 the last 5.75
15.7 5.64 is very strong
16.0 5.53 very a little less than
17.3 in 5.13
17.8 4.97 is very strong
19.1 in 4.65
20.6 4.30 is very strong
21.0 a little less than in the of 4.22
21.4 4.15 very a little less than
22.1 a little less than in the of 4.02
22.5 a little less than in the of 3.94
23.4 in 3.79
23.8 a little less than in the of 3.73
24.2 in 3.68
24.6 a little less than in the of 3.61
24.8 a little less than in the of 3.58
25.3 3.52 is very strong
26.0 3.42 very a little less than
26.4 a little less than in the of 3.37
26.9 3.31 very a little less than
27.3 3.27 very a little less than
27.6 a little less than in the of 3.23
28.0 in 3.18
28.9 3.08 very a little less than
29.4 3.03 very a little less than
30.3 2.95 very a little less than
31.2 the last 2.87
31.7 2.82 very a little less than
32.1 2.79 very a little less than
32.7 2.73 very a little less than
33.4 2.68 very a little less than
33.8 2.65 very a little less than
34.0 2.63 very a little less than
34.5 a little less than in the of 2.60
34.9 a little less than in the of 2.57;
B) the J variant of formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1/2 and s be 0, it is characterized in that having following X-ray powder pattern:
2 θ [°] d
Figure C018047470004C1
Intensity
5.6 a little less than in the of 15.7
8.61 0.2 is very strong
10.7 a little less than in the of 8.2
11.3 a little less than in the of 7.8
12.1 a little less than in the of 7.3
13.1 a little less than in the of 6.7
13.6 6.5 very a little less than
14.4 in 6.2
15.7 5.64 very a little less than
16.0 a little less than in the of 5.53
16.3 a little less than in the of 5.42
17.4 a little less than in the of 5.09
17.9 in 4.96
18.2 4.86 very a little less than
19.3 in 4.60
20.3 in 4.37
21.0 a little less than in the of 4.24
21.6 4.11 is very strong
22.5 3.95 very a little less than
22.8 a little less than in the of 3.90
23.3 3.81 very a little less than
24.0 in 3.71
24.5 a little less than in the of 3.62
25.3 3.52 very a little less than
26.0 the last 3.43
26.4 a little less than in the of 3.37
26.8 3.32 very a little less than
27.3 a little less than in the of 3.27
30.4 2.94 very a little less than
31.7 in 2.82;
C) the K variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 0, it is characterized in that having following X-ray powder pattern:
2 θ [°] d
Figure C018047470005C1
Intensity
6.6 a little less than in the of 13.4
8.8 10.1 very a little less than
9.5 9.3 is very strong
11.4 a little less than in the of 7.8
12.9 6.9 very a little less than
13.3 6.7 very a little less than
15.7 5.63 very a little less than
16.6 in 5.35
19.0 a little less than in the of 4.66
20.0 4.44 very a little less than
20.4 a little less than in the of 4.35
21.5 the last 4.12
22.6 the last 3.94
22.9 3.87 very a little less than
23.7 a little less than in the of 3.76
24.6 in 3.61
25.5 3.49 very a little less than
26.2 3.40 very a little less than;
D) the C variant of formula I compound, wherein M is a sodium, n is 1, r be 0 and s be 1, it is characterized in that having following X-ray powder pattern:
2 θ [°] d
Figure C018047470006C1
Intensity
6.7 in 13.1
8.11 1.0 is very strong
10.1 a little less than in the of 8.8
11.4 7.7 is very strong
12.2 7.2 is very strong
12.7 a little less than in the of 7.0
13.9 a little less than in the of 6.4
14.3 the last 6.2
14.9 a little less than in the of 5.96
15.0 a little less than in the of 5.90
15.7 the last 5.64
16.2 a little less than in the of 5.47
16.6 in 5.34
17.1 a little less than in the of 5.19
18.5 a little less than in the of 4.79
18.7 in 4.74
19.1 4.64 very a little less than
19.5 the last 4.55
19.9 a little less than in the of 4.47
20.4 the last 4.35
20.8 in 4.26
21.5 a little less than in the of 4.13
21.9 4.06 very a little less than
22.7 3.92 is very strong
23.0 a little less than in the of 3.87
23.5 3.79 is very strong
24.2 a little less than in the of 3.67
24.6 in 3.61
24.9 the last 3.58
25.7 a little less than in the of 3.47
26.9 3.32 very a little less than
27.5 in 3.24
28.4 a little less than in the of 3.14
28.6 a little less than in the of 3.12
29.1 a little less than in the of 3.07
29.3 the last 3.04
30.1 2.97 very a little less than
30.6 2.92 very a little less than
31.0 a little less than in the of 2.88
31.7 a little less than in the of 2.82
32.3 2.77 very a little less than
32.7 2.74 very a little less than
33.3 a little less than in the of 2.69
33.7 2.66 very a little less than; And
E) the I variant of formula I compound, wherein M is a sodium, n is 1, L is an oxolane, r be 1 and s be 1, it is characterized in that having following X-ray powder pattern:
2 θ [°] d
Figure C018047470008C1
Intensity
7.6 a little less than in the of 11.6
9.0 9.8 very a little less than
11.0 8.0 is very strong
11.6 in 7.6
13.3 the last 6.7
13.7 6.4 very a little less than
14.0 a little less than in the of 6.3
14.4 6.1 very a little less than
15.3 in 5.80
15.6 5.66 very a little less than
16.2 the last 5.47
17.3 5.12 very a little less than
17.4 5.08 very a little less than
18.3 a little less than in the of 4.84
18.6 a little less than in the of 4.76
19.8 the last 4.47
20.1 a little less than in the of 4.40
21.1 in 4.21
21.2 in 4.19
21.4 4.15 very a little less than
22.2 4.00 very a little less than
22.6 3.93 very a little less than
23.2 in 3.84
23.9 3.72 is very strong
24.8 in 3.58
25.3 in 3.52
26.9 3.32 very a little less than
27.2 3.28 very a little less than
27.5 3.25 very a little less than
28.7 3.11 very a little less than
29.0 3.07 very a little less than
30.2 2.95 very a little less than
31.2 a little less than in the of 2.86
31.7 2.82 very a little less than
32.6 2.75 very a little less than
34.9 a little less than in the of 2.57
36.0 2.49 very a little less than.
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DE102004014620A1 (en) 2004-03-25 2005-10-06 Bayer Cropscience Ag 2,4,6-phenyl-substituted cyclic ketoenols
WO2008058617A2 (en) * 2006-11-13 2008-05-22 Syngenta Participations Ag Herbicidal synergistic composition comprising a sulfonylurea herbicide and pretilachlor
CN102283235B (en) * 2011-09-15 2014-03-19 安徽丰乐农化有限责任公司 Postemergence formulated herbicide used for cotton field
CN105746556A (en) * 2016-03-14 2016-07-13 南京华洲药业有限公司 Weeding composition containing trifloxysulfuron and isoxaflutole and application of weeding composition containing trifloxysulfuron and isoxaflutole
CN105746554A (en) * 2016-03-14 2016-07-13 南京华洲药业有限公司 Herbicidal composition with trifloxysulfuron and pyrithiobac-sodium and application thereof
CN105746555A (en) * 2016-03-14 2016-07-13 南京华洲药业有限公司 Weeding composition containing trifloxysulfuron and ethoxysulfuron and application of weeding composition containing trifloxysulfuron and ethoxysulfuron
CN105746573B (en) * 2016-03-14 2018-05-22 南京华洲药业有限公司 A kind of Herbicidal combinations and its application containing trifloxysulfuron and anilofos
CN105746552A (en) * 2016-03-14 2016-07-13 南京华洲药业有限公司 Herbicidal composition with trifloxysulfuron and tepraloxydim and application thereof
CN105746549A (en) * 2016-03-14 2016-07-13 南京华洲药业有限公司 Weeding composition containing trifloxysulfuron and sethoxydim and application of weeding composition containing trifloxysulfuron and sethoxydim
CN105746553A (en) * 2016-03-14 2016-07-13 南京华洲药业有限公司 Herbicidal composition with trifloxysulfuron and prometryn and application thereof
CN114271290B (en) * 2021-12-10 2023-03-31 湖北泰盛化工有限公司 Ternary weeding composition and application thereof
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002606A (en) * 1981-10-16 1991-03-26 Ciba-Geigy Corporation Optically active N-(1'-methyl-2'-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline as herbicide
US5457085A (en) * 1992-11-16 1995-10-10 Sandoz Ltd. Optical isomer of dimethenamid
WO1997041112A1 (en) * 1996-04-25 1997-11-06 Novartis Ag Sulfonylurea salts as herbicides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4544401A (en) * 1979-10-22 1985-10-01 E. I. Du Pont De Nemours And Company Agricultural pyridinesulfonamides
AU708918B2 (en) * 1997-01-28 1999-08-19 Syngenta Participations Ag Herbicidal synergistic composition and method of weed control
PE20010035A1 (en) * 1999-03-01 2001-02-15 Novartis Ag HERBICIDE COMPOSITION BASED ON PYRIDYLSULFONYLUREA SALTS

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002606A (en) * 1981-10-16 1991-03-26 Ciba-Geigy Corporation Optically active N-(1'-methyl-2'-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline as herbicide
US5457085A (en) * 1992-11-16 1995-10-10 Sandoz Ltd. Optical isomer of dimethenamid
WO1997041112A1 (en) * 1996-04-25 1997-11-06 Novartis Ag Sulfonylurea salts as herbicides

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